SYNTHESIS OF 3-HYDROXY-2-NAPHTHOIC ACID ANILIDE CATALYZED BY PHOSPHORUS (III) COMPOUNDS IN VARIOUS MEDIA
Catalysis with phosphorus P(III) compounds (phosphorus trichloride and phosphorous acid) in the acylation of aniline with 3=hydroxy=2=naphthoic acid in various media (toluene, octane, chlorobenzene, para=xylene, ortho=xylene, ortho=chlorotoluene, mesitylene, pseudocumene, n.=deсan, ortho= dichlo...
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| Date: | 2023 |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2023
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oai:ojs2.1444248.nisspano.web.hosting-test.net:article-5402023-06-23T03:47:41Z SYNTHESIS OF 3-HYDROXY-2-NAPHTHOIC ACID ANILIDE CATALYZED BY PHOSPHORUS (III) COMPOUNDS IN VARIOUS MEDIA Shteinberg, Leon phosphorus trichloride, phosphorous acid, 3=hydroxyl=2=naphthoic acid, 3=hydroxyl=2=naphthoic acid anilide, aniline, solvents, catalysis Catalysis with phosphorus P(III) compounds (phosphorus trichloride and phosphorous acid) in the acylation of aniline with 3=hydroxy=2=naphthoic acid in various media (toluene, octane, chlorobenzene, para=xylene, ortho=xylene, ortho=chlorotoluene, mesitylene, pseudocumene, n.=deсan, ortho= dichlorobenzene, mixtures of ortho=xylene with nitrobenzene) upon boiling and vigorous distillation of water leads to the formation of 3=hydroxy=2=naphthoic acid anilide. With an increase in the reaction temperature in the range from 111 (toluene) to 170 °C (pseudo cumene), a monotonous increase in the initial rate of formation of the target product is observed. In this case, the temperature dependence of the logarithm of the velocity obeys the Arrhenius equation, and the activation energy Ea is 66.2 kJ/mol. Higher-boiling n.=decane (175 °С) and ortho=dichlorobenzene (180 °С) fall out of this dependence, in which the initial rate of formation of anilide 3=hydroxy=2=naphthoic acid, compared with that for pseudocumene (170 °С), decreases. The latter may be due to the decomposition or oxidation of the catalyst at such a high temperature with the transition of P(III) to P(V), which does not have catalytic activity. The interaction of aniline with 3=hydroxyl=2=naphthoic acid proceeds as a series of sequential and parallel reactions in which, in addition to 3=hydroxyl=2= naphthoic acid anilide, 3=aniline=2=naphthoic acid and its anilide are formed as impurities. The most acceptable solvents are ortho=xylene and ortho=chlorotoluene with boiling points of 146 and 156°C, in which the yield of the target product is up to 98%. Below 146 °C the reaction proceeds at a relatively low rate; above 156°C the amount of impurities increases significantly, mainly in parallel with an increase in the reaction temperature, and the maximum yield of 3=hydroxyl=2=naphthoic acid anilide decreases. This requires its additional purification, significantly complicating the technological process. The addition of 10–20% by volume of nitrobenzene to ortho=xylene leads to an increase in the yield of 3=oxy=2=naphthoic acid anilide by 1.25–1.42 times in the temperature range of 146–148°C with increasing solvent polarity (ε), respectively, from 2.3 to 7.64. This may be due to an increase in the quantity of the monomers of the catalyst and/or 3=oxy=2=naphthoic acid and aniline in reaction mass and the speed of water separation. V.I.Vernadsky Institute of General and Inorganic Chemistry 2023-04-28 Article Article Organic chemistry Органическая xимия Органічна xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/540 10.33609/2708-129X.89.03.2023.55-69 Ukrainian Chemistry Journal; Vol. 89 No. 3 (2023): Ukrainian Chemistry Journal; 55-69 Украинский химический журнал; Том 89 № 3 (2023): Ukrainian Chemistry Journal; 55-69 Український хімічний журнал; Том 89 № 3 (2023): Український хімічний журнал; 55-69 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/540/275 |
| institution |
Ukrainian Chemistry Journal |
| baseUrl_str |
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| datestamp_date |
2023-06-23T03:47:41Z |
| collection |
OJS |
| language |
English |
| topic_facet |
phosphorus trichloride phosphorous acid 3=hydroxyl=2=naphthoic acid 3=hydroxyl=2=naphthoic acid anilide aniline solvents catalysis |
| format |
Article |
| author |
Shteinberg, Leon |
| spellingShingle |
Shteinberg, Leon SYNTHESIS OF 3-HYDROXY-2-NAPHTHOIC ACID ANILIDE CATALYZED BY PHOSPHORUS (III) COMPOUNDS IN VARIOUS MEDIA |
| author_facet |
Shteinberg, Leon |
| author_sort |
Shteinberg, Leon |
| title |
SYNTHESIS OF 3-HYDROXY-2-NAPHTHOIC ACID ANILIDE CATALYZED BY PHOSPHORUS (III) COMPOUNDS IN VARIOUS MEDIA |
| title_short |
SYNTHESIS OF 3-HYDROXY-2-NAPHTHOIC ACID ANILIDE CATALYZED BY PHOSPHORUS (III) COMPOUNDS IN VARIOUS MEDIA |
| title_full |
SYNTHESIS OF 3-HYDROXY-2-NAPHTHOIC ACID ANILIDE CATALYZED BY PHOSPHORUS (III) COMPOUNDS IN VARIOUS MEDIA |
| title_fullStr |
SYNTHESIS OF 3-HYDROXY-2-NAPHTHOIC ACID ANILIDE CATALYZED BY PHOSPHORUS (III) COMPOUNDS IN VARIOUS MEDIA |
| title_full_unstemmed |
SYNTHESIS OF 3-HYDROXY-2-NAPHTHOIC ACID ANILIDE CATALYZED BY PHOSPHORUS (III) COMPOUNDS IN VARIOUS MEDIA |
| title_sort |
synthesis of 3-hydroxy-2-naphthoic acid anilide catalyzed by phosphorus (iii) compounds in various media |
| description |
Catalysis with phosphorus P(III) compounds (phosphorus trichloride and phosphorous acid) in the acylation of aniline with 3=hydroxy=2=naphthoic acid in various media (toluene, octane, chlorobenzene, para=xylene, ortho=xylene, ortho=chlorotoluene, mesitylene, pseudocumene, n.=deсan, ortho= dichlorobenzene, mixtures of ortho=xylene with nitrobenzene) upon boiling and vigorous distillation of water leads to the formation of 3=hydroxy=2=naphthoic acid anilide. With an increase in the reaction temperature in the range from 111 (toluene) to 170 °C (pseudo cumene), a monotonous increase in the initial rate of formation of the target product is observed. In this case, the temperature dependence of the logarithm of the velocity obeys the Arrhenius equation, and the activation energy Ea is 66.2 kJ/mol.
Higher-boiling n.=decane (175 °С) and ortho=dichlorobenzene (180 °С) fall out of this dependence, in which the initial rate of formation of anilide 3=hydroxy=2=naphthoic acid, compared with that for pseudocumene (170 °С), decreases. The latter may be due to the decomposition or oxidation of the catalyst at such a high temperature with the transition of P(III) to P(V), which does not have catalytic activity.
The interaction of aniline with 3=hydroxyl=2=naphthoic acid proceeds as a series of sequential and parallel reactions in which, in addition to 3=hydroxyl=2= naphthoic acid anilide, 3=aniline=2=naphthoic acid and its anilide are formed as impurities.
The most acceptable solvents are ortho=xylene and ortho=chlorotoluene with boiling points of 146 and 156°C, in which the yield of the target product is up to 98%. Below 146 °C the reaction proceeds at a relatively low rate; above 156°C the amount of impurities increases significantly, mainly in parallel with an increase in the reaction temperature, and the maximum yield of 3=hydroxyl=2=naphthoic acid anilide decreases. This requires its additional purification, significantly complicating the technological process.
The addition of 10–20% by volume of nitrobenzene to ortho=xylene leads to an increase in the yield of 3=oxy=2=naphthoic acid anilide by 1.25–1.42 times in the temperature range of 146–148°C with increasing solvent polarity (ε), respectively, from 2.3 to 7.64. This may be due to an increase in the quantity of the monomers of the catalyst and/or 3=oxy=2=naphthoic acid and aniline in reaction mass and the speed of water separation. |
| publisher |
V.I.Vernadsky Institute of General and Inorganic Chemistry |
| publishDate |
2023 |
| url |
https://ucj.org.ua/index.php/journal/article/view/540 |
| work_keys_str_mv |
AT shteinbergleon synthesisof3hydroxy2naphthoicacidanilidecatalyzedbyphosphorusiiicompoundsinvariousmedia |
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2025-09-24T17:43:50Z |
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2025-09-24T17:43:50Z |
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